Diiron Azadithiolate Complexes with Bridging Phosphine Ligand dppf: Synthesis and Characterization

Reaction of complex [(mu-SCH2)(2)NCH2CO2Me]Fe-2(CO)(6) (A) with 1,1(')-bis(diphenylphosphino)ferrocene (dppf) in the presence of the decarbonylating agent Me(3)NOa (TM) 2H(2)O gave complex [(mu-SCH2)(2)NCH2CO2MeFe2(CO)(5)](2)[(eta (5)-Ph2PC5H4)(2)Fe] (1) in 72 % yields, whereas complex [(mu-SCH2)(2)NPhFe2(CO)(5)](2)[(eta (5)-Ph2PC5H4)(2)Fe] (2) was produced by reaction of [(mu-SCH2)(2)NPh]Fe-2(CO)(6) (B) with dppf in toluene at reflux in 41 % yield. The new complexes 1 and 2 were characterized by elemental analysis, IR, and H-1 (P-31, C-13) NMR spectroscopy as well as by single crystal X-ray diffraction analysis. In the crystal structures of 1 and 2, the dppf ligand resides in an apical position of the square-pyramidal geometry of the neighbouring Fe atoms and the crystal structures were stabilized by the intermolecular C-H center dot center dot center dot O hydrogen bonds.